EP0189836B1 - Basic azo dyes - Google Patents
Basic azo dyes Download PDFInfo
- Publication number
- EP0189836B1 EP0189836B1 EP86100832A EP86100832A EP0189836B1 EP 0189836 B1 EP0189836 B1 EP 0189836B1 EP 86100832 A EP86100832 A EP 86100832A EP 86100832 A EP86100832 A EP 86100832A EP 0189836 B1 EP0189836 B1 EP 0189836B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- hydrogen
- oder
- nhc
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000987 azo dye Substances 0.000 title description 2
- -1 cycloaliphatic Chemical group 0.000 claims description 87
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000000460 chlorine Chemical group 0.000 claims description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000004442 acylamino group Chemical group 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 18
- 239000000975 dye Substances 0.000 description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229960000583 acetic acid Drugs 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 150000002431 hydrogen Chemical group 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 0 CCO*1CC*CC1 Chemical compound CCO*1CC*CC1 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical class NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-M methoxyacetate Chemical compound COCC([O-])=O RMIODHQZRUFFFF-UHFFFAOYSA-M 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KORHRZLLIUEBSB-UHFFFAOYSA-N n,n-diethyl-4-phenyl-1,3-thiazol-2-amine Chemical compound S1C(N(CC)CC)=NC(C=2C=CC=CC=2)=C1 KORHRZLLIUEBSB-UHFFFAOYSA-N 0.000 description 1
- VMWJCFLUSKZZDX-UHFFFAOYSA-N n,n-dimethylmethanamine Chemical compound [CH2]N(C)C VMWJCFLUSKZZDX-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B44/00—Azo dyes containing onium groups
- C09B44/02—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group
Definitions
- DE-A-2 050 246 discloses cationic azo dyes whose diazo component is derived from special aniline derivatives which have an alkoxycarbonyl radical, the alkyl group still having a substituted ammonium radical.
- R z. B preferred: C 2 H 4 or CH 2 CH (CH 3 ).
- Alkyl radicals R 1 and R 2 generally have 1 to 14 carbon atoms and can be, for example, by N-cycloalkylamino, N, N-di-C 1 - to C 5 -alkylamino, hydroxy or C 1 - to C 8 -alkoxy be substituted. Also worth mentioning are allyl, methallyl or C 5 - to C 8 -cycloalkyl.
- R 1 and R 2 together with the nitrogen can form, for example, the residues of the following heterocycles:
- Pyrrolidine, piperidine, morpholine, piperazine, which on the nitrogen through methyl, ethyl, n- and i-propyl, n-, i-, sec-butyl, 2-hydroxyethyl, 2-aminoethyl, 2- or 3-hydroxypropyl, 2nd - Or 3-aminopropyl may be substituted, imidazole, which may be substituted in the 2- and / or 4-position by methyl, ethyl, propyl or butyl or N-3- (C 1 - to C 12 ) -alkyl or vinyl -imidazole, which can still be substituted in the 2- and / or 4-position by methyl, ethyl, propyl or butyl.
- R 1 and R 2 are e.g. B .:
- Preferred heterocyclic radicals are for example those of:
- Morpholine piperidine, 4-methylpiperazine, 4-ethylpiperazine, 4-hydroxyethylpiperazine, 4- (2'-aminoethyl) piperazine, imidazole, 2-methylimidazole or 4-methylimidazole.
- the rest can also be a group of formula be.
- R 3 come z.
- C 1 - to C 12 -alkyl or C 2 - to C 4 -hydroxyalkyl such as methyl, ethyl, n- or i-propyl, n- or i-butyl, n- or i-amyl, n- or i- Hexal, octyl, 2-ethylhexyl, decyl, dodecyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, hydroxybutyl, benzyl, CH 2 CH 2 (OH) CH 2 CI or CH 2 CH (OH) CH 2 0H.
- R 3 is preferably C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or benzyl.
- Methyl, ethyl and C 2 - or C 3 -hydroxyalkyl are particularly preferred for R3.
- radicals carrying R 6 and R 7 are phenylene radicals of the formula II
- the radicals of the formula II are in particular the 1,4 - phenylene radicals which are monosubstituted or disubstituted by methyl, methoxy, ethoxy or acylamino, acylamino, for example for NHCOCH 3 , NHCOC 2 H 5 , NHCOC 6 H 5 , NHCONH 2 , NHCON (CH 3 ) 2 or NHCONHC 6 H 5 .
- NHCOCH 3 or NHCONHC 6 H 5 and the combination CH 3 / OCH 3 are particularly preferred.
- R 8 are, for example, optionally chlorine, bromine, cyano, hydroxyl, C 1 -C 4 -alkoxy, C i -C 4 -alkoxycarbonyl, C 1 -C 4 -alkyl mercapto, phenoxy, sulfophenoxy, phenylmercapto, Amino, N-mono- or N, N-di-C 1 to C 4 alkylamino, phenylamino, sulfophenylamino, C 1 to C 4 alkanoylamino or sulfoethylamino substituted C 1 to C 4 alkyl, vinyl, cyclohexyl, optionally by fluorine, chlorine, bromine, hydroxy, Ci to C 4 alkoxy, ⁇ -C 1 to C 4 alkanoyloxyethoxy, ⁇ -cyanoethoxy, ⁇ -carboxylethyloxy, ⁇ -C 1 to C 4 -alkoxycarbony
- R 8 radicals are preferably C 1 -C 4 -alkyl, ⁇ -carboxymethyl or optionally by chlorine, bromine, methyl, ethyl, C 1 -C 4 -alkoxy, ⁇ -cyanoethoxy, ⁇ -carboxylethoxy, phenoxy, sulfophenoxy, C 1 - to C 4 -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino substituted phenyl.
- R 9 and R 10 are, for example, C 1 -C 8 -alkyl radicals which are still interrupted by oxygen and by Hydroxy, carboxy, cyan, chlorine, bromine, phenyl, C 1 - to C 8 -alkoxy, C 1 - to C 4 -alkanoyloxy, C 1 - to C 4 -alkoxycarbonyl, C 1 - to C 4 -alkanoylamino, acetyl, C 1 to C 4 alkylaminocarbonyloxy, arylaminocarbonyloxy, C 1 to C 4 alkoxycarbonyloxy or phenoxycarbonyloxy may be substituted, allyl, methallyl, propargyl, cyclohexyl, phenyl-C 1 to C 5 -alkyl or optionally by fluorine, chlorine, Bromine, C 1 - to C 4 -alkoxycarbonyl, nitro or C 1 - to C 4 -alkanoylamino substitute
- individual radicals R 9 and R 10 are, for example: hydrogen, methyl, ethyl, propyl, butyl, ⁇ -hydroxyethyl, ⁇ -methoxyethyl, y-methoxypropyl, ⁇ -cyanoethyl, ⁇ -carbomethoxyethyl, ⁇ -carboethoxyethyl, ⁇ - Acetoxyethyl, ⁇ -ethoxycarbonylethyl, y-acetylaminopropyt, phenoxycarbonyloxyethyl, phenylaminocarbonyloxyethyl, butylaminocarbonyloxyethyl, benzyl, ⁇ -phenethyl, phenyl, sulfophenyl, disulfophenyl, acetylaminophenyl, carboxyphenyl, cyanphenyl, chlorophenyl or sulfeth
- R 9 and R 10 together with the nitrogen are, for example, oligomethyleneimino optionally interrupted by 0, N or S, such as, for example, pyrrolidino, piperidino, morpholino, piperazino, ⁇ -methylpiperazino, hexamethyleneimino or thiomorpholino-S-dioxide.
- R 9 and R 10 independently of one another, preference is given to C 1 - to C 8 -alkyl, by hydroxy, carboxy, hydroxysulfonyl, cyano, phenyl, C 1 - to C 8 -alkoxy, phenoxy, C 1 - to C 4 -alkanoyloxy, C 1 - to C 4 -alkoxycarbonyl, C 1 - to C 4 -alkanoylamino or C 1 - to C 4 -alkoxycarbonyloxy-substituted C 2 - to C B -alkyl, allyl, phenyl-C 1 - to C 5 -alkyl or optionally phenyl substituted by chlorine, bromine, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy, cyan or carbamoyl and for (NR 9 R 10 ) pyrrolidino, piperidino, piperazino or morpholino.
- Anions A ⁇ are z.
- Amino compounds of the formulas can be used to prepare the compounds of the formulas Ia and Ib and diazotize and with the coupling component of the formula implement.
- the compounds of the formulas Ia and Ib are suitable for dyeing acid-modified fibers such as polyacrylonitrile or polyesters, leather and in particular paper.
- paper can also be printed with printing inks that contain aqueous acidic solutions from la and ib.
- the bases or salts with longer-chain carboxylic or sulfonic acids such as oleic acid or dodecylbenzenesulfonic acid, they also come, for. B. for ballpoint pen pastes, solvent dyes or non-aqueous printing inks.
- the dyes are also readily soluble in water and organic solvents, making them suitable for the production of liquid concentrates.
- the dye can be dissolved with glacial acetic acid and water to a liquid setting. It colors paper stock intensely blue in shade no. 13, Color Index Hue Indication Chart. The wastewater is colorless. The colored paper can be bleached with hypochlorite. The fastness to bleeding against aqueous soda solution and water is excellent even in deep tones, and very good against aqueous acetic acid.
- dyes can be produced from the corresponding halogenated or sulfochlorinated derivatives of isatoic anhydride, which dye paper blue.
- Diazo component prepared according to Example 1 is distilled. 21 parts in 100 parts of toluene are added dropwise at 60 ° C. with 13 parts of dimethyl sulfate. The mixture is stirred for an hour at this temperature, cooled to room temperature and the precipitate is filtered off with suction. After drying, the diazotization equivalent is 355 g / val (theory 334 g / val). The connection corresponds to the formula
- Example 2 After diazotization and coupling as in Example 1, the mixture is made alkaline with sodium hydroxide solution, the aqueous phase is decanted from the greasy dye and dissolved in aqueous glacial acetic acid.
- a suspension of 50 parts of bleached sulfate pulp of about 30 ° SR in 2000 parts of water at pH 7 are 2 parts of a 10 percent.
- acetic acid solution of the dye from Example 1 added.
- the mixture is stirred for 15 minutes at 20 to 25 ° C and then diluted to 0.2% solids content with water.
- paper sheets are produced on a laboratory sheet former and the sheets are dried at 10 ° C. for 5 minutes. Blue colored leaves are obtained.
- the waste water is colorless, the bleeding fastness against Water and aqueous soda solution excellent, good against acetic acid.
- An absorbent paper web made from unsized paper is drawn at 40-50 ° C. through a dye solution which is composed of 0.5 part of dye from Example 1, 0.5 part of starch, 3 parts of acetic acid and 96 parts of water. The excess dye solution is pressed between two rollers. The dried paper web is colored blue.
- the dyes from the other examples can also be used analogously.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Plural Heterocyclic Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polymerization Catalysts (AREA)
- Coloring (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Aus der DE-A-2 050 246 sind kationische Azofarbstoffe bekannt, deren Diazokomponente sich von speziellen Anilinderivaten ableitet, die einen Alkoxycarbonylrest aufweisen, wobei die Alkylgruppe noch einen substituierten Ammoniumrest besitzt.DE-A-2 050 246 discloses cationic azo dyes whose diazo component is derived from special aniline derivatives which have an alkoxycarbonyl radical, the alkyl group still having a substituted ammonium radical.
Es wurden nun neue Verbindungen der Formeln
- Y Wasserstoff, Chlor, Brom oder Nitro,
- R gegebenenfalls durch Sauerstoff oder
- m die Zahlen 0 oder 1,
- R1 und R2 unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Aralkyl oder Aryl oder
- R1 und R2 zusammen mit dem Stickstoff einen Heterocyclus,
- R3 Wasserstoff oder gegebenenfalls substituiertes Alkyl,
- R6 und R7 unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkoxy oder Acylamino,
- RB Wasserstoff, Acetyl, Benzoyl oder einen aliphatischen, cycloaliphatischen, aromatischen oder heterocyclischen Rest und
- R9 und R10 unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes Alkyl oder Cycloalkyl oder zusammen mit dem Stickstoff einen Heterocyclus und
- A⊖ ein Anion bedeuten, wobei
- R5 für Wasserstoff oder C1- bis C4-Alkyl steht und der Rest
- auch für einen 1-Pyridylrest stehen kann.
- Y is hydrogen, chlorine, bromine or nitro,
- R optionally by oxygen or
- m the numbers 0 or 1,
- R 1 and R 2 are independently hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl or
- R 1 and R 2 together with the nitrogen form a heterocycle,
- R 3 is hydrogen or optionally substituted alkyl,
- R 6 and R 7 independently of one another are hydrogen, optionally substituted alkyl, alkoxy or acylamino,
- R B is hydrogen, acetyl, benzoyl or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical and
- R 9 and R 10 independently of one another hydrogen, optionally substituted alkyl or cycloalkyl or together with the nitrogen a heterocycle and
- A⊖ is an anion, where
- R 5 represents hydrogen or C 1 to C 4 alkyl and the rest
- can also represent a 1-pyridyl radical.
Gegebenenfalls substituierte Alkylenreste R haben z.B. 2 bis 10 C-Atome, bevorzugt sind C2-oder C3-Reste.
- Im einzelnen sind beispielsweise zu nennen:
- C2H4OC2H4, C3H6C3H6, C3H6OC2H4OC3H6,
- C3H6OC4H8OC3H6, C3H60C2H40C2H40C3H6,
- C2H4NHC2H4, C2H4NHC3H6, C3H6NHC3H6,
- C3H6NHC2H4NHC3H6, C3H6NHC6H12NHC3H6,
- The following can be mentioned in detail, for example:
- C 2 H 4 OC 2 H 4 , C 3 H 6 C 3 H 6 , C 3 H 6 OC 2 H 4 OC 3 H 6 ,
- C 3 H 6 OC 4 H 8 OC 3 H 6 , C 3 H 6 0C 2 H 4 0C 2 H 4 0C 3 H 6 ,
- C 2 H 4 NHC 2 H 4 , C 2 H 4 NHC 3 H 6 , C 3 H 6 NHC 3 H 6 ,
- C 3 H 6 NHC 2 H 4 NHC 3 H 6 , C 3 H 6 NHC 6 H 12 NHC 3 H 6 ,
Für R sind z. B. bevorzugt: C2H4 oder CH2CH(CH3).For R z. B. preferred: C 2 H 4 or CH 2 CH (CH 3 ).
Alkylreste R1 und R2 haben in der Regel 1 bis 14 C-Atome und können z.B. durch N-Cycloalkylamino, N,N-Di-C1- bis -C5-alkylamino, Hydroxy oder C1- bis C8-Alkoxy substituiert sein. Ferner sind Allyl, Methallyl oder C5- bis C8-Cycloalkyl zu erwähnen.Alkyl radicals R 1 and R 2 generally have 1 to 14 carbon atoms and can be, for example, by N-cycloalkylamino, N, N-di-C 1 - to C 5 -alkylamino, hydroxy or C 1 - to C 8 -alkoxy be substituted. Also worth mentioning are allyl, methallyl or C 5 - to C 8 -cycloalkyl.
Im einzelnen seien beispielsweise neben den bereits aufgeführten folgende Reste genannt:In particular, the following radicals may be mentioned in addition to those already listed:
Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, n-Amyl, i-Amyl, n-Hexyl, i-Hexyl, Heptyl, Octyl, 2-Ethylhexyl, Decyl, Dodecyl, Tridecyl, Tetradecyl, 2-Hydroxyethyl, 2- oder 3-Hydroxypropyl, Hydroxybutyl, Cyclopentyl, Cyclohexyl oder Cyclooctyl, N,N-Dimethylaminoethyl, N,N-Diethylaminoethyl, N,N-Dipropylaminoethyl, N,N-Dibutyl- aminoethyl, 3-(N,N-Dimethylamino)-propyl, 3-(N,N-Diethylamino)-propyl, 3-(N,N-Dipropylami- no)-propyl oder 3-(N,N-Dibutylamino)-propyl, N-Cyclohexylaminoethyl, 3-(N-Cyclohexylamino)-propyl, 3-(N-Cyclooctylamino)-propyl, N-Methyl-N-cyclohexylaminoethyl, 3-(N-Methyl-N-cyclohexyl- amino)-propyl, Benzyl, Phenethyl, Phenyl oderTolyl.Methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-amyl, i-amyl, n-hexyl, i-hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, Tetradecyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, hydroxybutyl, cyclopentyl, cyclohexyl or cyclooctyl, N, N-dimethylaminoethyl, N, N-diethylaminoethyl, N, N-dipropylaminoethyl, N, N-dibutylaminoethyl, 3- ( N, N-dimethylamino) propyl, 3- (N, N-diethylamino) propyl, 3- (N, N-dipropylamino) propyl or 3- (N, N-dibutylamino) propyl, N-cyclohexylaminoethyl , 3- (N-cyclohexylamino) propyl, 3- (N-cyclooctylamino) propyl, N-methyl-N-cyclohexylaminoethyl, 3- (N-methyl-N-cyclohexylamino) propyl, benzyl, phenethyl, phenyl or Tolyl.
R1 und R2 können zusammen mit dem Stickstoff z.B. die Reste folgender Heterocyclen bilden:R 1 and R 2 together with the nitrogen can form, for example, the residues of the following heterocycles:
Pyrrolidin, Piperidin, Morpholin, Piperazin, das am Stickstoff durch Methyl, Ethyl, n- und i-Propyl, n-, i-, sec.-Butyl, 2-Hydroxyethyl, 2-Aminoethyl, 2-oder 3-Hydroxypropyl, 2- oder 3-Aminopropyl substituiert sein kann, Imidazol, das in 2- und/oder 4-Stellung durch Methyl, Ethyl, Propyl oder Butyl substituiert sein kann oder N-3-(C1- bis C12)-Alkyl-oder Vinyl-imidazol, das in 2- und/oder 4-Stellung noch durch Methyl, Ethyl, Propyl oder Butyl substituiert sein kann.Pyrrolidine, piperidine, morpholine, piperazine, which on the nitrogen through methyl, ethyl, n- and i-propyl, n-, i-, sec-butyl, 2-hydroxyethyl, 2-aminoethyl, 2- or 3-hydroxypropyl, 2nd - Or 3-aminopropyl may be substituted, imidazole, which may be substituted in the 2- and / or 4-position by methyl, ethyl, propyl or butyl or N-3- (C 1 - to C 12 ) -alkyl or vinyl -imidazole, which can still be substituted in the 2- and / or 4-position by methyl, ethyl, propyl or butyl.
Bevorzugte Reste R1 und R2 sind z. B.:Preferred radicals R 1 and R 2 are e.g. B .:
Methyl, Ethyl, n-Propyl, i-Propyl, C2- oder C3-Hydroxyalkyl oder Cyclohexyl.Methyl, ethyl, n-propyl, i-propyl, C 2 - or C 3 -hydroxyalkyl or cyclohexyl.
Bevorzugte heterocyclische Reste
Morpholin, Piperidin, 4-Methylpiperazin, 4-Ethylpiperazin, 4-Hydroxyethylpiperazin, 4-(2'-Aminoethyl)-piperazin, Imidazol, 2-Methylimidazol oder 4-Methylimidazol.Morpholine, piperidine, 4-methylpiperazine, 4-ethylpiperazine, 4-hydroxyethylpiperazine, 4- (2'-aminoethyl) piperazine, imidazole, 2-methylimidazole or 4-methylimidazole.
Der Rest
Für R3 kommen daneben z. B. C1- bis C12-Alkyl oder C2- bis C4-Hydroxyalkyl wie Methyl, Ethyl, n-oder i-Propyl, n- oder i-Butyl, n- oder i-Amyl, n-oder i-Hexal, Octyl, 2-Ethylhexyl, Decyl, Dodecyl, 2-Hydroxyethyl, 2- oder 3-Hydroxypropyl, Hydroxybutyl, Benzyl, CH2CH2(OH)CH2CI oder CH2CH(OH)CH20H in Betracht.For R 3 come z. B. C 1 - to C 12 -alkyl or C 2 - to C 4 -hydroxyalkyl such as methyl, ethyl, n- or i-propyl, n- or i-butyl, n- or i-amyl, n- or i- Hexal, octyl, 2-ethylhexyl, decyl, dodecyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, hydroxybutyl, benzyl, CH 2 CH 2 (OH) CH 2 CI or CH 2 CH (OH) CH 2 0H.
Vorzugsweise steht R3 für C1- bis C4-Alkyl, C2- bis C4-Hydroxyalkyl oder Benzyl.R 3 is preferably C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or benzyl.
Für R3 sind Methyl, Ethyl und C2- oder C3-Hydroxyalkyl besonders bevorzugt.Methyl, ethyl and C 2 - or C 3 -hydroxyalkyl are particularly preferred for R3.
Die R6 und R7 tragenden Reste sind Phenylenreste der Formel II
Reste der Formel II sind insbesondere die durch Methyl, Methoxy, Ethoxy oder Acylamino einfach oder zweifach substituierten 1,4-Phenylenreste, wobei Acylamino z.B. für NHCOCH3, NHCOC2H5, NHCOC6H5, NHCONH2, NHCON(CH3)2 oder NHCONHC6H5 steht. Besonders bevorzugt sind NHCOCH3 oder NHCONHC6H5 sowie die Kombination CH3/OCH3.The radicals of the formula II are in particular the 1,4 - phenylene radicals which are monosubstituted or disubstituted by methyl, methoxy, ethoxy or acylamino, acylamino, for example for NHCOCH 3 , NHCOC 2 H 5 , NHCOC 6 H 5 , NHCONH 2 , NHCON (CH 3 ) 2 or NHCONHC 6 H 5 . NHCOCH 3 or NHCONHC 6 H 5 and the combination CH 3 / OCH 3 are particularly preferred.
Reste R8 sind beispielsweise gegebenenfalls durch Chlor, Brom, Cyan, Hydroxy, C1- bis C4-Alkoxy, Ci- bis C4-Alkoxycarbonyl, C1- bis C4-Alkyl- mercapto, Phenoxy, Sulfophenoxy, Phenylmercapto, Amino, N-mono- oder N,N-di-C1- bis C4- alkylamino, Phenylamino, Sulfophenylamino, C1- bis C4-Alkanoylamino oder Sulfoethylamino substituiertes C1- bis C4-Alkyl, Vinyl, Cyclohexyl, gegebenenfalls durch Fluor, Chlor, Brom, Hydroxy, Ci- bis C4-Alkoxy, β-C1- bis C4 Alkanoyloxyethoxy, β-Cyanethoxy, β-Carboxylethyloxy, β-C1- bis C4-Aikoxycarbonylethoxy, Phenoxy, Sulfophenoxy, C1- bis C4-Alkylmercapto, Phenylmercapto, Amino, β-C1- bis C4-Alkanoylamino, Benzoylamino, C1- bis C4-Alkylamino oder -Dialkylamino, Phenylamino, Sulfophenylamino, C1- bis C4-Alkylsul- fonylamino oder Phenylsulfonylamino substituiertes Phenyl, Thienyl oder Thiazolyl.R 8 are, for example, optionally chlorine, bromine, cyano, hydroxyl, C 1 -C 4 -alkoxy, C i -C 4 -alkoxycarbonyl, C 1 -C 4 -alkyl mercapto, phenoxy, sulfophenoxy, phenylmercapto, Amino, N-mono- or N, N-di-C 1 to C 4 alkylamino, phenylamino, sulfophenylamino, C 1 to C 4 alkanoylamino or sulfoethylamino substituted C 1 to C 4 alkyl, vinyl, cyclohexyl, optionally by fluorine, chlorine, bromine, hydroxy, Ci to C 4 alkoxy, β-C 1 to C 4 alkanoyloxyethoxy, β-cyanoethoxy, β-carboxylethyloxy, β-C 1 to C 4 -alkoxycarbonylethoxy, phenoxy, sulfophenoxy , C 1 - to C 4 -alkylmercapto, phenylmercapto, amino, β-C 1 - to C 4 -alkanoylamino, benzoylamino, C 1 - to C 4 -alkylamino or -dialkylamino, phenylamino, sulfophenylamino, C 1 - to C 4 - Alkylsulfonylamino or phenylsulfonylamino substituted phenyl, thienyl or thiazolyl.
Einzelne Reste R8 sind z.B.:
- CH3, C2H5, CH2CI, CH2CN, CH20H, CH2-CH2Cl,
- CH2-CH2OH, CH2-CH2CN, CH2-COOCH3,
- CH2COOC2H5, -CH20CH3, -CH2OC2H5, CH2SCH3,
- CH2N(CH3)2, C6H5OCH2, C6H5, ClC6H4, BrC6H4,
- FC6H4, Cl2C6H3, CH3C6H4, (CH3)2C6H3, CH3OC6H4,
- C2H5OC6H4, NCC2H4OC6H4, CH3OOC·C2H4OC6H4,
- H2NCOC2H4OC6H4, CH3COOC2H4OC6H4,
- HOC2H40C6H4, HOC6H4, C6H5OC6H4, CH3SC6H4,
- C6H5SC6H4, NC-C2H4SC6H4, CH3CONHC6H4,
- C2H5CONHC6H4, H2N-C6H4, HOC2H4NHC6H4,
- (C2H5)2NC6H4, CH3SO2NHC6H4, C6H5SO2NHC6H4,
- C6H5NHC6H4,
- CH 3 , C 2 H 5 , CH 2 CI, CH 2 CN, CH 2 0H, CH 2 -CH 2 Cl,
- CH 2 -CH 2 OH, CH 2 -CH 2 CN, CH 2 -COOCH 3 ,
- CH 2 COOC 2 H 5 , -CH 2 0CH 3 , -CH 2 OC 2 H 5 , CH 2 SCH 3 ,
- CH 2 N (CH 3 ) 2 , C 6 H 5 OCH 2 , C 6 H 5 , ClC 6 H 4 , BrC 6 H 4 ,
- FC 6 H 4 , Cl 2 C 6 H 3 , CH 3 C 6 H 4 , (CH 3 ) 2 C 6 H 3 , CH 3 OC 6 H 4 ,
- C 2 H 5 OC 6 H 4 , NCC 2 H 4 OC 6 H 4 , CH 3 OOC · C 2 H 4 OC 6 H 4 ,
- H 2 NCOC 2 H 4 OC 6 H 4 , CH 3 COOC 2 H 4 OC 6 H 4 ,
- HOC 2 H 4 0C 6 H 4 , HOC 6 H 4 , C 6 H 5 OC 6 H 4 , CH 3 SC 6 H 4 ,
- C 6 H 5 SC 6 H 4 , NC-C 2 H 4 SC 6 H 4 , CH 3 CONHC 6 H 4 ,
- C 2 H 5 CONHC 6 H 4 , H 2 NC 6 H 4 , HOC 2 H 4 NHC 6 H 4 ,
- (C 2 H 5 ) 2 NC 6 H 4 , CH 3 SO 2 NHC 6 H 4 , C 6 H 5 SO 2 NHC 6 H 4 ,
- C 6 H 5 NHC 6 H 4 ,
Reste R8 sind bevorzugt C1- bis C4-Alkyl, β-Carboxymethyl oder gegebenenfalls durch Chlor, Brom, Methyl, Ethyl, C1- bis C4-Alkoxy, β-Cyanethoxy, β-Carboxylethoxy, Phenoxy, Sulfophenoxy, C1- bis C4-Alkanoylamino, Phenylamino, Sulfophenylamino oder Sulfoethylamino substituiertes Phenyl.R 8 radicals are preferably C 1 -C 4 -alkyl, β-carboxymethyl or optionally by chlorine, bromine, methyl, ethyl, C 1 -C 4 -alkoxy, β-cyanoethoxy, β-carboxylethoxy, phenoxy, sulfophenoxy, C 1 - to C 4 -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino substituted phenyl.
Reste R9 und R10 sind z.B. C1- bis C8-Alkylreste, die noch durch Sauerstoff unterbrochen und durch Hydroxy, Carboxy, Cyan, Chlor, Brom, Phenyl, C1- bis C8-Alkoxy, C1- bis C4-Alkanoyloxy, C1- bis C4-Alkoxycarbonyl, C1- bis C4-Alkanoylamino, Acetyl, C1- bis C4-Alkylaminocarbonyloxy, Arylaminocarbonyloxy, C1- bis C4-Alkoxycarbonyloxy oder Phenoxycarbonyloxy substituiert sein können, Allyl, Methallyl, Propargyl, Cyclohexyl, Phenyl-C1- bis C5-alkyl oder gegebenenfalls durch Fluor, Chlor, Brom, C1- bis C4-Alkoxycarbonyl, Nitro oder C1- bis C4-Alkanoylamino substituiertes Phenyl.R 9 and R 10 are, for example, C 1 -C 8 -alkyl radicals which are still interrupted by oxygen and by Hydroxy, carboxy, cyan, chlorine, bromine, phenyl, C 1 - to C 8 -alkoxy, C 1 - to C 4 -alkanoyloxy, C 1 - to C 4 -alkoxycarbonyl, C 1 - to C 4 -alkanoylamino, acetyl, C 1 to C 4 alkylaminocarbonyloxy, arylaminocarbonyloxy, C 1 to C 4 alkoxycarbonyloxy or phenoxycarbonyloxy may be substituted, allyl, methallyl, propargyl, cyclohexyl, phenyl-C 1 to C 5 -alkyl or optionally by fluorine, chlorine, Bromine, C 1 - to C 4 -alkoxycarbonyl, nitro or C 1 - to C 4 -alkanoylamino substituted phenyl.
Einzelne Reste R9 und R10 sind neben den bereits genannten beispielsweise: Wasserstoff, Methyl, Ethyl, Propyl, Butyl, β-Fiydroxyethyl, β-Methoxyethyl, y-Methoxypropyl, β-Cyanethyl, β-Carbomethoxyethyl, β-Carboethoxyethyl, β-Acetoxyethyl, β-Ethoxycarbonylethyl, y-Acetylaminopropyt, Phenoxycarbonyloxyethyl, Phenylaminocarbonyloxyethyl, Butylaminocarbonyloxyethyl, Benzyl, β-Phenethyl, Phenyl, Sulfophenyl, Disulfophenyl, Acetylaminophenyl, Carboxyphenyl, Cyanphenyl, Chlorphenyl oder Sulfethyl.In addition to those already mentioned, individual radicals R 9 and R 10 are, for example: hydrogen, methyl, ethyl, propyl, butyl, β-hydroxyethyl, β-methoxyethyl, y-methoxypropyl, β-cyanoethyl, β-carbomethoxyethyl, β-carboethoxyethyl, β- Acetoxyethyl, β-ethoxycarbonylethyl, y-acetylaminopropyt, phenoxycarbonyloxyethyl, phenylaminocarbonyloxyethyl, butylaminocarbonyloxyethyl, benzyl, β-phenethyl, phenyl, sulfophenyl, disulfophenyl, acetylaminophenyl, carboxyphenyl, cyanphenyl, chlorophenyl or sulfethyl.
R9 und R10 zusammen mit dem Stickstoff sind z.B. gegebenenfalls durch 0, N oder S unterbrochenes Oligomethylenimino, wie z.B. Pyrrolidino, Piperidino, Morpholino, Piperazino, a-Methylpiperazino, Hexamethylenimino oder Thiomorpholino-S-dioxid.R 9 and R 10 together with the nitrogen are, for example, oligomethyleneimino optionally interrupted by 0, N or S, such as, for example, pyrrolidino, piperidino, morpholino, piperazino, α-methylpiperazino, hexamethyleneimino or thiomorpholino-S-dioxide.
Bevorzugt sind für R9 und R10 unabhängig voneinander C1- bis C8-Alkyl, durch Hydroxy, Carboxy, Hydroxysulfonyl, Cyan, Phenyl, C1- bis C8-Alkoxy, Phenoxy, C1- bis C4-Alkanoyloxy, C1- bis C4-Alkoxycarbonyl, C1- bis C4-Alkanoylamino oder C1- bis C4-Alkoxycarbonyloxy substituiertes C2- bis CB-Alkyl, Allyl, Phenyl-C1- bis C5-Alkyl oder gegebenenfalls durch Chlor, Brom, C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Cyan oder Carbamoyl substituiertes Phenyl sowie für (NR9R10) Pyrrolidino, Piperidino, Piperazino oder Morpholino.For R 9 and R 10, independently of one another, preference is given to C 1 - to C 8 -alkyl, by hydroxy, carboxy, hydroxysulfonyl, cyano, phenyl, C 1 - to C 8 -alkoxy, phenoxy, C 1 - to C 4 -alkanoyloxy, C 1 - to C 4 -alkoxycarbonyl, C 1 - to C 4 -alkanoylamino or C 1 - to C 4 -alkoxycarbonyloxy-substituted C 2 - to C B -alkyl, allyl, phenyl-C 1 - to C 5 -alkyl or optionally phenyl substituted by chlorine, bromine, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy, cyan or carbamoyl and for (NR 9 R 10 ) pyrrolidino, piperidino, piperazino or morpholino.
Anionen A⊖ sind z. B.: Chlorid, Bromid, Hydrogensulfat, Sulfat, Nitrat, Phosphat, Hydrogenphosphat, Dihydrogenphosphat, Carbonat, Hydrogencarbonat, Tetrachlorozinkat, Aminosulfonat, Methylsulfonat, Methylsulfat, Ethylsulfat, Formiat, Acetat, Hydroxyacetat, Aminoacetat, Methoxyacetat, Propionat, Lactat, Maleinat, Malonat, Citrat, Benzoat, Phthalat, Benzolsulfonat, Toluolsulfonat, Oleat oder Dodecylbenzolsulfonat.Anions A⊖ are z. For example: chloride, bromide, hydrogen sulfate, sulfate, nitrate, phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate, tetrachlorozincate, aminosulfonate, methyl sulfonate, methyl sulfate, ethyl sulfate, formate, acetate, hydroxyacetate, amino acetate, methoxyacetate, malateate, malateate, malateate, malionate , Citrate, benzoate, phthalate, benzenesulfonate, toluenesulfonate, oleate or dodecylbenzenesulfonate.
Zur Herstellung der Verbindungen der Formeln la und Ib kann man Aminoverbindungen der Formeln
Einzelheiten der Herstellung können den Beispielen entnommen werden, in denen sich Angaben über Teile und Prozente, sofern nichts anders vermerkt, auf das Gewicht beziehen.Details of the production can be found in the examples, in which information on parts and percentages, unless stated otherwise, relate to the weight.
Die Verbindungen der Formeln la und Ib eignen sich zum Färben von sauer modifizierten Fasern wie Polyacrylnitril oder Polyestern, Leder und insbesondere Papier. Auch lässt sich insbesondere Papier mit Druckfarben bedrucken, die wässrige saure Lösungen von la und Ib enthalten. In Form der Basen oder Salze mit längerkettigen Carbon-oder Sulfonsäuren wie Ölsäure oder Dodecylbenzolsulfosäure kommen sie auch z. B. für Kugelschreiberpasten, Solventfarbstoffe oder nicht wässrige Druckfarben in Betracht. Mit entsprechenden Anionen sind die Farbstoffe auch leicht in Wasser und organischen Lösungsmitteln löslich, so dass sie sich zur Herstellung von flüssigen Konzentraten eignen.The compounds of the formulas Ia and Ib are suitable for dyeing acid-modified fibers such as polyacrylonitrile or polyesters, leather and in particular paper. In particular, paper can also be printed with printing inks that contain aqueous acidic solutions from la and ib. In the form of the bases or salts with longer-chain carboxylic or sulfonic acids such as oleic acid or dodecylbenzenesulfonic acid, they also come, for. B. for ballpoint pen pastes, solvent dyes or non-aqueous printing inks. With the appropriate anions, the dyes are also readily soluble in water and organic solvents, making them suitable for the production of liquid concentrates.
Von besonderer Bedeutung sind Verbindungen der Formeln (la) und (Ib), in denen bedeuten:
- Y: Wasserstoff oder Nitro;
- R: C2H4, C3H6, -CH(CH3)CH2 oder C4H8;
- R1 und R2: H, CH3, C2H5, n-, i-C3H7, n-, i-, sec.-C4H9, C2H40CH3,
- R3: CH3, C2H5 oder C2H40H;
- R6 und R7: H, CH3, OCH3, OC2H5.
- R8: C1- bis C4-Alkyl, β-Carboxymethyl oder gegebenenfalls durch Chlor, Brom, Methyl, Ethyl, Cl- bis C4-Alkoxy, β-Cyanethoxy, β-Carboxylethoxy, Phenoxy, Sulfophenoxy, C1- bis C4-Alkanoylamino, Phenylamino, Sulfophenylamino oder Sulfoethylamino substituiertes Phenyl. Besonders bevorzugt ist Phenyl.
- R9 und R10: C1- bis C8-alkyl, durch Hydroxy, Carboxy, Hydroxysulfonyl, Cyan, Phenyl, C1- bis C8-Alkoxy, Phenoxy, Cl- bis C4-Alkanoyloxy, C1- bis C4-Alkoxycarbonyl, Cl- bis C4-Alkanoylamino oder Cl- bis C4-Alkoxycarbonyloxy substituiertes C2- bis C8-Alkyl, Allyl, Phenyl-C1- bis C5-Alkyl oder gegebenenfalls durch Chlor, Brom, Cl- bis C4-Alkyl, Cl- bis C4-Alkoxy, Cyan oder Carbamoyl substituiertes Phenyl und NR9R10 gegebenenfalls durch 0 oder N unterbrochenes Oligomethylenimino. Besonders bevorzugt für R9 und R10 sind Wasserstoff, Phenyl, Methyl, Ethyl oder Propyl, sowie für NR9R10 Morpholino, Piperazino oder Piperidino.
- Y: hydrogen or nitro;
- R: C 2 H 4 , C 3 H 6 , -CH (CH 3 ) CH 2 or C 4 H 8 ;
- R 1 and R 2 : H, CH 3 , C 2 H 5 , n-, iC 3 H 7 , n-, i-, sec.-C 4 H 9 , C 2 H 4 0CH 3 ,
- R 3 : CH 3 , C 2 H 5 or C 2 H 4 0H;
- R 6 and R 7 : H, CH 3 , OCH 3 , OC 2 H 5 .
- R 8 : C 1 - to C 4 -alkyl, β-carboxymethyl or optionally by chlorine, bromine, methyl, ethyl, C l - to C 4 -alkoxy, β-cyanoethoxy, β-carboxylethoxy, phenoxy, sulfophenoxy, C 1 - to C 4 -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino substituted phenyl. Phenyl is particularly preferred.
- R 9 and R 10 : C 1 - to C 8 -alkyl, by hydroxy, carboxy, hydroxysulfonyl, cyano, phenyl, C 1 - to C 8 -alkoxy, phenoxy, C 1 - to C 4 -alkanoyloxy, C 1 - bis C 4 alkoxycarbonyl, C 1 to C 4 alkanoylamino or C 1 to C 4 alkoxycarbonyloxy substituted C 2 to C 8 alkyl, allyl, phenyl C 1 to C 5 alkyl or optionally by chlorine, bromine , C 1 to C 4 alkyl, C 1 to C 4 alkoxy, cyano or carbamoyl substituted phenyl and NR 9 R 10 optionally interrupted by 0 or N oligomethyleneimino. Hydrogen, phenyl, methyl, ethyl or propyl are particularly preferred for R 9 and R 10 , and morpholino, piperazino or piperidino for NR 9 R 10 .
208 Teile Anthranilsäure-2'-dimethylaminoethyl- ester werden mit 500 Teilen Eis angerührt. Unter Aussenkühlung werden 500 Teile konz. Salzsäure, dann unterhalb 5°C 300 Volumenteile 23-proz. wässrige Natriumnitritlösung zugegeben. Bei 10-15°C rührt man drei Stunden, zerstört danach überschüssiges Nitrit durch Zugabe von Amidosulfonsäure und tropft eine Lösung von 129 Teilen 1-Naphthylamin in 250 Teilen Eisessig zu. Man lässt über Nacht auf Raumtemperatur kommen, saugt ab und wäscht mit 20-proz. Kochsalzlösung. Der Filterkuchen wird mit 500 Teilen Eis und 200 Teilen konz. Salzsäure angerührt. 300 Volumenteile 23-proz. wässrige Natriumnitritlösung werden zugetropft, wobei der pH-Wert durch Salzsäurezugabe unter 1 gehalten wird. Man rührt eine Stunde bei Raumtemperatur nach, zerstört überschüssiges Nitrit und tropft dann eine Lösung von 250 Teilen 2-Diethylamino-4-phenyl-1,3-thiazol in 200 Teilen Eisessig zu. Durch Zugabe von Natriumacetat wird ein pH von ungefähr 4,5 eingestellt und zwei Stunden nachgerührt. Danach saugt man ab, wäscht mit 20-proz. wässriger Kochsalzlösung, rührt den Filterkuchen in Ammoniakwasser auf, saugt wieder ab und wäscht mit Wasser. Nach der Gefriertrocknung werden 1203 g der mit Salz verunreinigten Farbstoffs der Formel
Der Farbstoff lässt sich mit Eisessig und Wasser zu einer Flüssigeinstellung auflösen. Er färbt Papierstoff intensiv blau im Farbton No. 13, Colour Index Hue Indication Chart. Das Abwasser istfarblos. Das gefärbte Papier lässt sich mit Hypochlorit bleichen. Die Ausbluteechtheit gegen wässrige Sodalösung und Wasser ist auch in tiefen Tönen hervorragend, die gegen wässrige Essigsäure sehr gut.The dye can be dissolved with glacial acetic acid and water to a liquid setting. It colors paper stock intensely blue in shade no. 13, Color Index Hue Indication Chart. The wastewater is colorless. The colored paper can be bleached with hypochlorite. The fastness to bleeding against aqueous soda solution and water is excellent even in deep tones, and very good against aqueous acetic acid.
Analog dem beschriebenen Verfahren lassen sich weitere Farbstoffe herstellen, die im Farbton und der Affinität zu Papierstoff weitgehend der obigen Verbindung entsprechen.
Analog Beispiel 1 lassen sich aus den entsprechenden halogenierten bzw. sulfochlorierten Derivaten des Isatosäureanhydrids weitere Farbstoffe herstellen, die Papier blau färben.
Herstellung der Diazokomponente: Nach Beispiel 1 hergestellte Diazokomponente wird destilliert. 21 Teile werden in 100 Teilen Toluol tropfenweise bei 60°C mit 13 Teilen Dimethylsulfat versetzt. Man rührt eine Stunde bei dieser Temperatur nach, kühlt auf Raumtemperatur und saugt den Niederschlag ab. Nach der Trocknung beträgt das Diazotierungsäquivalent 355 g/val (Theorie 334 g/ val). Die Verbindung entspricht der FormelPreparation of the diazo component: Diazo component prepared according to Example 1 is distilled. 21 parts in 100 parts of toluene are added dropwise at 60 ° C. with 13 parts of dimethyl sulfate. The mixture is stirred for an hour at this temperature, cooled to room temperature and the precipitate is filtered off with suction. After drying, the diazotization equivalent is 355 g / val (theory 334 g / val). The connection corresponds to the formula
Nach Diazotierung und Kupplung analog Beispiel 1 stellt man mit Natronlauge alkalisch, dekantiert die wässrige Phase vom schmierigen Farbstoff und löst in wässrigem Eisessig. Der Farbstoff färbt Papierstoff blau bei mässiger Abwasseranfärbung und entspricht nun der Formel
Einer Suspension von 50 Teilen gebleichtem Sulfatzellstoff von ca. 30° SR in 2000 Teilen Wasser bei pH 7 werden 2 Teile einer 10-proz. essigsauren Lösung des Farbstoffs aus Beispiel 1 zugegeben. Das Gemisch wird 15 Minuten bei 20 bis 25°C gerührt und dann mit Wasser auf 0,2% Feststoffgehalt verdünnt. Mit dieser Suspension werden auf einem Laborblattbildner Papierblätter hergestellt und die Blätter 5 Minuten bei 10°C getrocknet. Man erhält blau gefärbte Blätter. Das Abwasser ist farblos, die Ausblutechtheit gegen Wasser und wässrige Sodalösung hervorragend, gegen Essigsäure gut.A suspension of 50 parts of bleached sulfate pulp of about 30 ° SR in 2000 parts of water at pH 7 are 2 parts of a 10 percent. acetic acid solution of the dye from Example 1 added. The mixture is stirred for 15 minutes at 20 to 25 ° C and then diluted to 0.2% solids content with water. With this suspension, paper sheets are produced on a laboratory sheet former and the sheets are dried at 10 ° C. for 5 minutes. Blue colored leaves are obtained. The waste water is colorless, the bleeding fastness against Water and aqueous soda solution excellent, good against acetic acid.
Verwendung der Farbstoffe aus den anderen Beispielen erbringt ähnlich gute Färbeergebnisse.Use of the dyes from the other examples gives similarly good coloring results.
In eine gerührte Suspension aus 100 Teilen eines Gemisches von 70% gebleichtem Kiefernsulfatzellstoff und 30% gebleichtem Birkensulfatzellstoff mit ca. 30° SR im Gesamtstoff in 2000 Teilen Wasser werden 1,0 Teile des Vermahlungsproduktes aus 90% Farbstoff nach Beispiel 1 und 10% Amidosulfonsäure eingestreut und 10 Minuten verrührt. Nach Verdünnung mit Wasser auf 0,2% Feststoffgehalt werden auf einem Laborblattbildner Papierblätter hergestellt und die Blätter 5 Minuten bei 100°C getrocknet. Man erhält gleichmässig blau gefärbte Blätter mit hervorragender Ausblutechtheit gegen Wasser. Verwendung von Vermahlungsprodukten der Farbstoffe aus Beispiel 2-70 mit Amidosulfonsäure erbringt ähnlich gute Färbeergebnisse.In a stirred suspension of 100 parts of a mixture of 70% bleached pine sulfate pulp and 30% bleached birch sulfate pulp with approx. 30 ° SR in total in 2000 parts of water, 1.0 part of the ground product of 90% dye according to Example 1 and 10% amidosulfonic acid are sprinkled in and stirred for 10 minutes. After dilution with water to a solids content of 0.2%, paper sheets are produced on a laboratory sheet former and the sheets are dried at 100 ° C. for 5 minutes. You get uniform blue colored leaves with excellent bleeding resistance to water. Use of grinding products of the dyes from Example 2-70 with amidosulfonic acid produces similarly good dyeing results.
Eine saugfähige Papierbahn aus ungeleimten Papier wird bei 40-50°C durch eine Farbstofflösung gezogen, die sich zusammensetzt aus 0,5 Teilen Farbstoff aus Beispiel 1, 0,5 Teilen Stärke, 3 Teilen Essigsäure und 96 Teilen Wasser. Die überschüssige Farbstofflösung wird zwischen zwei Walzen abgepresst. Die getrocknete Papierbahn ist blau gefärbt.An absorbent paper web made from unsized paper is drawn at 40-50 ° C. through a dye solution which is composed of 0.5 part of dye from Example 1, 0.5 part of starch, 3 parts of acetic acid and 96 parts of water. The excess dye solution is pressed between two rollers. The dried paper web is colored blue.
Analog können auch die Farbstoffe aus den anderen Beispielen eingesetzt werden.The dyes from the other examples can also be used analogously.
Claims (2)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853502693 DE3502693A1 (en) | 1985-01-26 | 1985-01-26 | BASIC AZO DYES |
DE3502693 | 1985-01-26 |
Publications (2)
Publication Number | Publication Date |
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EP0189836A1 EP0189836A1 (en) | 1986-08-06 |
EP0189836B1 true EP0189836B1 (en) | 1988-06-22 |
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ID=6260911
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP86100832A Expired EP0189836B1 (en) | 1985-01-26 | 1986-01-22 | Basic azo dyes |
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US (1) | US4694075A (en) |
EP (1) | EP0189836B1 (en) |
JP (1) | JPS61176666A (en) |
DE (2) | DE3502693A1 (en) |
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DE4028630A1 (en) * | 1990-09-08 | 1992-03-12 | Basf Ag | DISAZO DYES, THEIR CLUTCH COMPONENTS FROM THE RANGE OF HYDROXYSULFONYLNAPHTHALINE STEMS |
DE19815945A1 (en) * | 1998-04-09 | 1999-10-14 | Basf Ag | Cationic sulfonic acid dyes |
CA2853279C (en) | 2011-10-24 | 2021-03-23 | Endo Pharmaceuticals Inc. | Cyclohexylamines |
Family Cites Families (3)
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US3020272A (en) * | 1959-05-25 | 1962-02-06 | Du Pont | Disazo dyes for acrylic and polyester fibers |
US3694426A (en) * | 1969-10-20 | 1972-09-26 | Gaf Corp | Cationic azo dyes |
GB1516978A (en) * | 1975-10-01 | 1978-07-05 | Ici Ltd | Disazo dyestuffs |
-
1985
- 1985-01-26 DE DE19853502693 patent/DE3502693A1/en not_active Withdrawn
-
1986
- 1986-01-21 US US06/820,018 patent/US4694075A/en not_active Expired - Fee Related
- 1986-01-22 DE DE8686100832T patent/DE3660332D1/en not_active Expired
- 1986-01-22 EP EP86100832A patent/EP0189836B1/en not_active Expired
- 1986-01-24 JP JP61012290A patent/JPS61176666A/en active Pending
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EP0189836A1 (en) | 1986-08-06 |
US4694075A (en) | 1987-09-15 |
JPS61176666A (en) | 1986-08-08 |
DE3502693A1 (en) | 1986-07-31 |
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